Block copolymers spontaneously assemble into various nanoscale structures such as spheres, cylinders, and lamellar structures according to the relative volumn ratio of each macromolecular block and their overall molecular weights. The self-assembled structures of block copolymer have been extensively investigated for the applications such as nanocomposites, photonic crystals, nanowires, magnetic-storage media, flash memory devices. However, the naturally formed nanostructures of block copolymers contain a high density of defects such that the practical applications for nanoscale devices have been limited. For the practical application of block copolymer nanostructures, a robust process to direct the assembly of block copolymers in thin film geometry is required to be established. To exploit self-assembly of block copolymer for the nanotechnology, it is indispensible to fabricate defect-free self-assembled nanostructure over an arbitrarily large area.